Manufacture and use of agricultural spray adjuvants for hard water conditions

ABSTRACT

The invention pertains to a method for manufacture and use of pesticides or agricultural spray adjuvants that counteracts the effects of hard water cat ions on anionic pesticides when applied in water spray solutions.

SUMMARY OF THE INVENTION

A mixture of strong mineral acids which would completely dissociate in water, including but not limited too; nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, and a polymer, preferred would be cationic, that is formulated as an agricultural spray adjuvant. The polymer in the formulation acts as a slow release mechanism for the acid. Polymeric forces on the mineral acid give the grower a practical mechanism for using mineral acid to counteract hard water cations. The adjuvant when mixed in a agricultural spray solution would act to tie up the hard water cations thus protecting any anionic pesticides, defoliants or plant growth regulators from reacting with the hard water cations such as Ca++, Mg++, Fe++ and becoming less effective as an agricultural chemicals. Thus the spray adjuvant would act to increase the apparent efficacy of the active ingredient being applied.

DETAILED DESCRIPTION OF THE INVENTION

Strong mineral acids were added to polymers in an attempt to deliver a controlled amount of acid into a spray solution. The acid would act as a “hard water cation scavenger”. The mixture would be an agronomic spray “hard water scavenger system”. In the preferred example sulfuric acid was added to tallow amine. Heat was given off indicating some reaction. However, pH measurements of spray mixtures taken before and after the addition of the “hard water scavenger system” shows that free acid still existed.

Knowing that any potential spray solution which could be contemplated would have to stay above a pH of which is higher that the pKa of most anionic pesticides. Differing mixtures of several examples where made up. Table 1, Table 2, Table 3. It was thought that this would be a more efficient method to condition the spray waters than current practice of using Ammonium Sulfate (AMS). However, the mixture would have to remain stable, not drop the pH below the pKa of anionic pesticides and work as well as or better than AMS. The efficiency would be gained by replacing large bags of dry AMS (17.5 lbs/100 gallons spray solution) or large volumes (5 gallon/100 gallons spray solution) of liquid AMS with 1 quart to 1 gallon per 100 gallons of spray solution with this kind of product. Also this liquid product would go into solution much faster than the current AMS goes into solution adding even more efficiency.

It was discovered that cationic macro molecules would make a stable mix with sulfuric acid. Also, cationic surfactant would act as a system that would deliver enough free acid to tie up hard water cations. While at the same time maintain the pH of the spray water above the pKa of the active ingredient being sprayed thus increasing the efficacy of the pesticide.

It was surprising to discover that these mixtures increased or maintained the efficacy of anionic pesticides under hard water conditions much better than the current practice of adding Ammonium Sulfate (FIG. 1 and FIG. 2). TABLE 1 Example 1 Formula 21-1 Water 65.9%/wt Tallow Am 3780 30.0 SAG 10 0.1 93% Sulfuric 4.0

TABLE 2 Example 2 Formula 21-2 Water 45.9%/wt Tallow Am 3780 50.0 SAG10 0.1 93% Sulfuric 4.0

TABLE 3 Example 3 INGREDIENT %/WT Diethylene Glycol 17.80 NP-10 50.00 AU391 30.00 93% Sulfuric Acid 2.00 SAG 10 [ 0.20 

1. A composition comprising of: (a) mineral or organic acids with the ability to react or associate with divalent and trivalent cat ions (hard water ions) to form salts and associations. (b) Cat ionic surfactant or cat ionic poly-molecules including poly amine surfactants combined with water soluble agricultural chemicals in an agricultural spray solution.
 2. The composition as claimed in claim 1, wherein said acid has the ability to completely or nearly completely dissociate in water and react with cat ions.
 3. The composition as claimed in claim 1, wherein said acid is sulfuric acid.
 4. The composition as claimed in claim 1, wherein said acid is Sodium Bisulfate
 5. The composition as claimed in claim 1, wherein said acid is perchloric acid.
 6. The composition as claimed in claim 1, wherein said acid is hydrobromic acid.
 7. The composition as claimed in claim 1, wherein said acid is hydroiodic acid.
 8. The composition as claimed in claim 1, wherein acid is hydrochloric acid.
 9. The composition as claimed in claim 1, wherein said acid is muriatic acid.
 10. The composition as claimed in claim 1, wherein said acid is nitric acid.
 11. The composition as claimed in claim 1, wherein said amine-containing poly molecule is a fatty amine alkoxylate
 12. The composition as claimed in claim 1, wherein said amine ethoxyolates
 13. The composition as claimed in claim 1, wherein said fatty amine alkoxylate is tallowamine ethoxylate.
 14. The composition as claimed in claim 1, wherein said fatty amine alkoxylate is cocoamine ethoxylate.
 15. The composition as claimed in claim 1, wherein said agricultural chemicals are anionic herbicides, fungicides, miticides, insecticides and plant growth regulators.
 16. The composition as claimed in claim 1, wherein said agricultural chemicals are natural acidic herbicides, fungicides, miticides, insecticides and plant growth regulators.
 17. The composition as claimed in claim 15, wherein said herbicide is a chlorinated carboxylic acid herbicide.
 18. The composition as claimed in claim 15, wherein said herbicide is glyphosate or a salt thereof.
 19. The composition as claimed in claim 15, wherein said herbicide is glufosinate or a salt thereof.
 20. The composition as claimed in claim 15, wherein said synthetic auxin is chloramben or dicamba or salts thereof.
 21. The composition as claimed in claim 15, wherein said herbicide is a synthetic auxin is a phenoxy carboxylic acid, 2,4-dichlorophenoxy acetic acid, 2,4,5-trichlorophenoxy acetic acid, 2,4-dichlorophenoxy butyric acid, clomeprop, dichlorprop, dichlorprop-P, monochlorophenoxy acetic acid, monochlorophenoxy butyric acid, mecoprop, or mecoprop-P or salts thereof.
 22. The composition as claimed in claim 15, wherein said herbicide is a synthetic auxin is 2,4-dichlorophenoxy acetic acid, 2,4,5-trichlorophenoxy acetic acid, 2,4-dichlorophenoxy butyric acid, clomeprop, dichlorprop, dichlorprop-P, monochlorophenoxy acetic acid, monochlorophenoxy butyric acid, mecoprop or mecoprop-P or salts thereof.
 23. The composition as claimed in claim 15, wherein said herbicide is a synthetic auxin is a pyridine carboxylic acid, clopyralid, fluroxypyr, picloram or triclopyr or salts thereof.
 24. The composition as claimed in claim 15, wherein said herbicide is a synthetic auxin is a quinoline carboxylic acid, quiclorac or quinmerac or salts thereof. 25 The composition as claimed in claim 15, wherein said heribicide is bentazon or salts thereof.
 26. The composition as claimed in claim 15, wherein said herbicide is a benzonitrile is bromoxynil, ioxynil or salts thereof.
 27. The composition as claimed in claim 15, wherein said herbicide is a imidazolinone is imazamethabenz, imazapyr, imazaquin, imazethapyr, or salts thereof.
 28. The composition as claimed in claim 15, wherein said herbicide is a PPO inhibitor fluoroglycofen, fomesafen or salts thereof.
 29. The composition as claimed in claim 15, wherein said herbicide is a cyclohexanedione is sethoxydim, clethodim, or salts thereof.
 30. The composition as claimed in claim 16, wherein said insecticides is a orgaonophosphate is malathion, parathion, guthion, lannate and phosmet.
 31. The composition as claimed in claim 16, wherein said insecticides is chloropyrifos. Dicofol and dimethoate.
 32. The composition as claimed in claim 16, wherein said fungicide is captan and carzole.
 33. The composition as claimed in claim 16, wherein said plant growth regulators is ethephon and Prohexadione calcium.
 34. The composition as claimed in claim 16, wherein said herbicide is a synthetic auxin is a phenoxy carboxylic acid, 2,4-dichlorophenoxy acetic acid, 2,4,5-trichlorophenoxy acetic acid, 2,4-dichlorophenoxy butyric acid, clomeprop, dichlorprop, dichlorprop-P, monochlorophenoxy acetic acid, monochlorophenoxy butyric acid, mecoprop, or mecoprop-P or ester thereof.
 35. The composition as claimed in claim 16, wherein said herbicide is a synthetic auxin is 2,4-dichlorophenoxy acetic acid, 2,4,5-trichlorophenoxy acetic acid, 2,4-dichlorophenoxy butyric acid, clomeprop, dichlorprop, dichlorprop-P, monochlorophenoxy acetic acid, monochlorophenoxy butyric acid, mecoprop or mecoprop-P or esters thereof.
 36. The composition as claimed in claim 16, wherein said herbicide is a Arloxyphenoxy acid is diclofop fenoxaprop, fluazifop, haloxyfop, or esters thereof
 37. A composition comprising of: (a) mineral or organic acids with the ability to react or associate with divalent and trivalent cat ions (hard water ions) to form associations with. (b) nonionic surfactants or poly-molecules with the ability of hydrogen bonding with acids included in group (a) combined with water soluble agricultural chemicals in an agricultural spray solution. 38 A composition as in claim 37 were the nonionic surfactant include: sugar ester type nonionic surfactants, fatty acid ester type nonionic surfactants, vegetable oil type nonionic surfactants, alcohol type nonionic surfactants, alkylphenol type nonionic surfactants, polyoxyethylene-polyoxypropylene block polymer type nonionic surfactants, bisphenol type nonionic surfactants, polyaromatic ring type nonionic surfactants, silicone type nonionic surfactants and fluorine type nonionic surfactants.
 39. The composition as claimed in claim 37, wherein said acid is sulfuric acid.
 40. The composition as claimed in claim 37, wherein said acid is Sodium Bisulfate
 41. The composition as claimed in claim 37, wherein said acid is perchloric acid.
 42. The composition as claimed in claim 37, wherein said acid is hydrobromic acid.
 43. The composition as claimed in claim 37, wherein said acid is hydroiodic acid.
 44. The composition as claimed in claim 37, wherein acid is hydrochloric acid.
 45. The composition as claimed in claim 37, wherein said acid is muriatic acid.
 46. The composition as claimed in claim 37, wherein said acid is nitric acid.
 47. The composition as claimed in claim 37, wherein said agricultural chemicals are anionic herbicides, fungicides, miticides, insecticides and plant growth regulators.
 48. The composition as claimed in claim 37, wherein said agricultural chemicals are natural acidic herbicides, fungicides, miticides, insecticides and plant growth regulators.
 49. The composition as claimed in claim 47, wherein said herbicide is a chlorinated carboxylic acid herbicide.
 50. The composition as claimed in claim 47, wherein said herbicide is glyphosate or a salt thereof.
 51. The composition as claimed in claim 47, wherein said herbicide is glufosinate or a salt thereof.
 52. The composition as claimed in claim 47, wherein said synthetic auxin is chloramben or dicamba or salts thereof.
 53. The composition as claimed in claim 47, wherein said herbicide is a synthetic auxin is a phenoxy carboxylic acid, 2,4-dichlorophenoxy acetic acid, 2,4,5-trichlorophenoxy acetic acid, 2,4-dichlorophenoxy butyric acid, clomeprop, dichlorprop, dichlorprop-P, monochlorophenoxy acetic acid, monochlorophenoxy butyric acid, mecoprop, or mecoprop-P or salts thereof.
 54. The composition as claimed in claim 47, wherein said herbicide is a synthetic auxin is 2,4-dichlorophenoxy acetic acid, 2,4,5-trichlorophenoxy acetic acid, 2,4-dichlorophenoxy butyric acid, clomeprop, dichlorprop, dichlorprop-P, monochlorophenoxy acetic acid, monochlorophenoxy butyric acid, mecoprop or mecoprop-P or salts thereof.
 55. The composition as claimed in claim 47, wherein said herbicide is a synthetic auxin is a pyridine carboxylic acid, clopyralid, fluroxypyr, picloram or triclopyr or salts thereof.
 56. The composition as claimed in claim 47, wherein said herbicide is a synthetic auxin is a quinoline carboxylic acid, quiclorac or quinmerac or salts thereof. 57 The composition as claimed in claim 47, wherein said heribicide is bentazon or salts thereof.
 58. The composition as claimed in claim 47, wherein said herbicide is a benzonitrile is bromoxynil, ioxynil or salts thereof.
 59. The composition as claimed in claim 47, wherein said herbicide is a imidazolinone is imazamethabenz, imazapyr, imazaquin, imazethapyr, or salts thereof.
 60. The composition as claimed in claim 47, wherein said herbicide is a PPO inhibitor fluoroglycofen, fomesafen or salts thereof.
 61. The composition as claimed in claim 47, wherein said herbicide is a cyclohexanedione is sethoxydim, clethodim, or salts thereof.
 62. The composition as claimed in claim 48, wherein said insecticides is a orgaonophosphate is malathion, parathion, guthion, lannate and phosmet.
 63. The composition as claimed in claim 48, wherein said insecticides is chloropyrifos. Dicofol and dimethoate.
 64. The composition as claimed in claim 48, wherein said fungicide is captan and carzole.
 65. The composition as claimed in claim 48, wherein said plant growth regulators is ethephon and Prohexadione calcium.
 66. The composition as claimed in claim 48, wherein said herbicide is a Arloxyphenoxy acid is diclofop fenoxaprop, fluazifop, haloxyfop, or esters thereof
 67. The composition as claimed in claim 48, wherein said herbicide is a synthetic auxin is a phenoxy carboxylic acid, 2,4-dichlorophenoxy acetic acid, 2,4,5-trichlorophenoxy acetic acid, 2,4-dichlorophenoxy butyric acid, clomeprop, dichlorprop, dichlorprop-P, monochlorophenoxy acetic acid, monochlorophenoxy butyric acid, mecoprop, or mecoprop-P or esters thereof.
 68. The composition as claimed in claim 48, wherein said herbicide is a synthetic auxin is 2,4-dichlorophenoxy acetic acid, 2,4,5-trichlorophenoxy acetic acid, 2,4-dichlorophenoxy butyric acid, clomeprop, dichlorprop, dichlorprop-P, monochlorophenoxy acetic acid, monochlorophenoxy butyric acid, mecoprop or mecoprop-P or esters thereof. 